CN109312188A

CN109312188A - Cation electric deposition paint composition

Info

Publication number: CN109312188A
Application number: CN201780033262.XA
Authority: CN
Inventors: 宫前治广; 太田达夫; 印部俊雄
Original assignee: Nippon Paint Co Ltd
Current assignee: Nippon Paint Co Ltd; Nippon Paint Automotive Coatings Co Ltd
Priority date: 2016-05-31
Filing date: 2017-05-30
Publication date: 2019-02-05
Anticipated expiration: 2037-05-30
Also published as: WO2017209091A1; EP3467056A4; JP6933645B2; JPWO2017209091A1; EP3467056B1; CN109312188B; EP3467056A1

Abstract

The issue of the present invention is to provide the cation electric deposition paint compositions that rust-preventing characteristic is excellent.The present invention provides cation electric deposition paint composition, it is the cation electric deposition paint composition containing amine-modified epoxy resin (A) curing agent (B) the 3rd group element compound (C) and cation or non-ionic resin (D), the number-average molecular weight of above-mentioned amine-modified epoxy resin (A) is 1,000 ~ 5, in the range of 000, the number-average molecular weight of above-mentioned cation or non-ionic resin (D) is 10,000 or more.

Description

Cation electric deposition paint composition

Technical field

The present invention relates to the cation electric deposition paint compositions that rust-preventing characteristic is excellent.

Background technique

Multiple films with various effects are formed on the surface of the coated articles such as metal base, while protecting coated article Assign graceful appearance.Generally, it as the film for assigning coated article anticorrosive property, is widely used through electrodeposition coating formation Electrodeposition coating.Electrodeposition coating can also carry out coating even with coated article thin with complex shape, It can automatically and continuously carry out coating, therefore the coated article large-scale and with complex shape as especially car body etc. Primary coat coating process is practical extensively.As such electrodeposition coating, it is widely used and is combined using cation electrodeposition coating The electrodeposition coating of object.

Other than requiring to assign coated article anticorrosive property, also require the surface state of film also good.It is applied as improving The method of the surface state of film has the method for the levelability that film is improved when forming film.For example, in the solidification of heating etc. When, film levelling is made by hot-fluid, the surface state of film can be improved.On the other hand, when coated article has edge part, the side It is also difficult when the coating of edge is even with electrodeposition coating.Moreover, because the levelling acts on and is added by hot-fluid Film is flowed by edge part sometimes when heat cure, therefore rust-preventing characteristic is deteriorated.Therefore, the coating of the coated article with edge part needs The method for improving the rust-preventing characteristic of edge part.

As the method for the rust-preventing characteristic for improving edge part, when it can be mentioned, for example by inhibiting electrodeposition coating to be heating and curing The flowing of electrodeposition coating caused by hot-fluid, it is ensured that the thus film thickness of edge part improves the method for rust-preventing characteristic.In this method, it is The flowing for inhibiting film caused by hot-fluid when being heating and curing, is taken through in electrodeposition coating composition and adds thickener Deng method, the method for improving viscosity of electrodeposition coating composition etc..But by being added in electrodeposition coating composition The levelability of thickener, film is deteriorated, and the surface state of flat part other than edge part etc. is deteriorated.Therefore, coated article side is taken into account The raising of the rust-preventing characteristic of edge and the raising (raising of film flatness) of film coated surface state are often difficult.

Cation electric deposition paint composition is described in Japanese Unexamined Patent Publication 2010-144104 bulletin (patent document 1), Be characterized in that, with amine-modified epoxy resin (b) blocked isocyanate compounds (c) of (a) amine concentration 1.0mol/kg or more into Gone cationic exchange amorphous silica particle be essential component.Describing the cation electric deposition paint composition can To form the excellent film ([0001] section etc.) of edges cover and flatness to coated article.It is described in the patent document 1 By the expression of the structural viscosity behavior from (c) ingredient, edges cover ([0029] section etc.) can be improved.Another party Face is aggregated, the flatness of obtained film has can since (c) ingredient is shot-like particle in electrodeposition coating composition It can be deteriorated.Such as the amount of (c) ingredient flatness if more is described in [0032] section etc. and is deteriorated.

It is described in Japanese Unexamined Patent Publication 5-239386 bulletin (patent document 2) to be special containing at least one kind of lanthanum compound The electrocoating paint composition of sign.It describes in patent document 2 by being compounded lanthanum compound in electrodeposition coating composition The excellent electrodeposition coating of anticorrosive property can be formed.But experiment shows only to contain lanthanum in electrocoating paint composition Because electrodeposition coating condition etc. cannot play excellent Corrosion Protection sometimes when closing object.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2010-144104 bulletin

Patent document 2: Japanese Unexamined Patent Publication 5-239386 bulletin.

Summary of the invention

Problems to be solved by the invention

The present invention is the invention to solve the above problems, and its purpose is to provide rust-preventing characteristic especially edge part rust-preventing characteristic is excellent Cation electric deposition paint composition.

The means solved the problems, such as

To solve the above-mentioned problems, the present invention provides following embodiments.

[1] cation electric deposition paint composition is containing amine-modified epoxy resin (A) curing agent (B) the 3rd race The cation electric deposition paint composition of element compound (C) and cation or non-ionic resin (D),

The number-average molecular weight of above-mentioned amine-modified epoxy resin (A) in the range of 1,000 ~ 5,000,

The number-average molecular weight of above-mentioned cation or non-ionic resin (D) is 10,000 or more.

[2] above-mentioned cation electric deposition paint composition, wherein above-mentioned cation or non-ionic resin (D) is selected from poly- 1 kind or a kind or more in acrylamide resin chitosan resin and amine-modified epoxy resin.

[3] above-mentioned cation electric deposition paint composition, wherein above-mentioned polyacrylamide resin is cationic poly- third Acrylamide resin.

[4] above-mentioned cation electric deposition paint composition, wherein above-mentioned 3rd group element compound (C) is selected from oxidation The mixture of the mixture lanthanum hydroxide and organic acid of lanthanum lanthanum hydroxide neodymia neodymium hydroxide lanthana and organic acid 1 kind or a kind or more in the mixture of the mixture neodymium hydroxide and organic acid of neodymia and organic acid.

[5] above-mentioned cation electric deposition paint composition, wherein the precipitation of above-mentioned cation electric deposition paint composition Electrodeposition coating 105 DEG C painting film viscosity be 10Pa s hereinafter, and

Above-mentioned precipitation electrodeposition coating is 200 ~ 5000Pa s in 105 DEG C of standing viscosity.

[6] above-mentioned cation electric deposition paint composition, wherein above-mentioned cation electric deposition paint composition is at 23 DEG C Viscosity of the coating be 10mPa s or less.

[7] above-mentioned cation electric deposition paint composition, wherein above-mentioned cation electric deposition paint composition also contains Bismuth compound, the average grain diameter of above-mentioned bismuth compound are 1 ~ 500nm.

[8] cured electrodeposition coating film-forming methods comprising impregnate quilt in above-mentioned cation electric deposition paint composition Coat carries out electrodeposition coating, is then heating and curing, and 25 ~ 50 μm of film thickness of cured electrodeposition is thus formed on coated article The process of film.

[9] above-mentioned coating film-forming methods, wherein above-mentioned coated article has edge part, and to the solidification electricity with formation When the coated article of electrodeposition coating film carries out salt spraytest, edge painting portion 1cm²Get rusty number occur less than 5/cm²。

Invention effect

Electrodeposition coating is carried out by using cation electric deposition paint composition of the invention, it is special rust-preventing characteristic can be formed Be edge part rust-preventing characteristic it is excellent and with excellent appearance of film cured electrodeposition film.

Specific embodiment

Cation electric deposition paint composition of the invention contains:

Amine-modified epoxy resin (A)

Curing agent (B)

3rd group element compound (C) and

Cation or non-ionic resin (D).

Here, the number-average molecular weight of above-mentioned amine-modified epoxy resin (A) is in the range of 1,000 ~ 5,000, above-mentioned sun from The number-average molecular weight of son or non-ionic resin (D) is 10,000 or more.Each ingredient is described in detail below.

Amine-modified epoxy resin (A)

Amine-modified epoxy resin (A) is the film formation resin for constituting electrodeposition coating.It is excellent as amine-modified epoxy resin (A) Oxirane ring organic amine compound in resin matrix is modified obtained cation-modified epoxy resin by choosing.Generally, positive Ion modification epoxy resin be by make oxirane ring in starting material molecular resin and primary amine secondary amine or tertiary amine and/or The amine of its hydrochlorate etc. reacts open loop and prepares.The typical example of starting material resin is as bisphenol-A Bisphenol F bisphenol S Phenol novolacsCresol novolak( Etc. polycyclic phenolic compounds and epichlorohydrin Reaction product the more glycidyl type epoxy resins of polyphenol.In addition, the example as other starting material resins, can enumerate The epoxy resin containing oxazolidone ring recorded in Japanese Unexamined Patent Publication 5-306327 bulletin.These epoxy resin can pass through two The lower alcohols such as the isocyanate group of diisocyanate cpd methanol/ethanol are blocked to obtain by isocyanate compound Double carbamate compound and epichlorohydrin react preparation.

Above-mentioned starting material resin can pass through 2 functionalities before the ring-opening reaction of the oxirane ring carried out using amine Polyester polyol polyether polyol 2 yuan of carboxylic acids of bisphenols etc. carry out chain elongation and use.Especially bisphenols can be in benefit It is used when the ring-opening reaction of the oxirane ring carried out with amine, carries out chain elongation.

In addition, similarly, it can be before the ring-opening reaction of the oxirane ring carried out using amine, with molecular weight or amine equivalent Adjusting thermal fluidity improvement etc. for the purpose of, to the ethylene oxide cycloaddition 2-Ethylhexyl Alcohol nonyl phenol second of a part The monohydroxy compound of the mono- mono- 2- ethylhexyl ether of 2- ethylhexyl ether ethylene glycol list n- butyl ether propylene glycol of glycol etc. is pungent The monocarboxylic acid compound of acid etc. and use.

As the example for the amine that can be used when oxirane ring open loop is imported amino, butylamine octyl can be enumerated Amine diethylamide dibutylamine methyl butyl amine monoethanolamine diethanol amine N- methylethanolamine triethylamine N, N- Primary amine secondary amine or tertiary amine and/or its hydrochlorate such as dimethyl benzyl amine N, N- dimethylethanolamine.Alternatively, it is also possible to use amino The secondary amine diethylenetriamines diketone containing primary amino group of the ketimides such as ehtylethanolamine methyl-isobutyl ketimide sealing end is sub- Amine.In order to make all oxirane ring open loops, these amines needs are at least reacted relative to oxirane ring with equivalent.

In the present invention, the number-average molecular weight of amine-modified epoxy resin (A) is in the range of 1,000 ~ 5,000.It is equal by number Molecular weight is 1,000 or more, and the solvent resistance of obtained cured electrodeposition film and the physical property of corrosion resistance etc. are good.It is another Aspect is 5,000 hereinafter, the viscosity-adjusting agent of amine-modified epoxy resin becomes easy by number-average molecular weight, can be well on Synthesis, in addition, the processing of the emulsion dispersion of obtained amine-modified epoxy resin (A) becomes easy.More preferable amine modified epoxy The range that the number-average molecular weight of resin (A) is 1,600 ~ 3,200.

It is noted that number-average molecular weight is the polystyrene measured by gel permeation chromatography (GPC) in this specification Convert number-average molecular weight.

In the range of the amine value of amine-modified epoxy resin (A) is preferably 20 ~ 100mgKOH/g.Pass through amine-modified epoxy resin (A) amine value is 20mgKOH/g or more, and the emulsion dispersion of the amine-modified epoxy resin (A) in electrodeposition coating composition is stablized Property is good.It on the other hand, is 100mgKOH/g hereinafter, the amount of the amino in cured electrodeposition film is suitable by amine value, it will not Reduce the water resistance of film.The amine value of amine-modified epoxy resin (A) is more preferably in the range of 20 ~ 80mgKOH/g.

In the range of the hydroxyl value of amine-modified epoxy resin (A) is preferably 50 ~ 400mgKOH/g.It is 50mgKOH/ by hydroxyl value G or more, the solidification of cured electrodeposition film become good.It on the other hand, is 400mgKOH/g by hydroxyl value hereinafter, solidification electricity is heavy The amount of remaining hydroxyl is suitable in product film, and the water resistance of film will not reduce.The hydroxyl value of amine-modified epoxy resin (A) is more preferable In the range of 100 ~ 300mgKOH/g.

It is 1,000 ~ 5,000 amine value by using number-average molecular weight in cation electric deposition paint composition of the invention For 20 ~ 100mgKOH/g and amine-modified epoxy resin (A) that hydroxyl value is 50 ~ 400mgKOH/g, there is that can to assign coated article excellent Corrosion resistance the advantages of.

It is noted that being used as amine-modified epoxy resin (A), amine value can be used together as needed and/or hydroxyl value is different Amine-modified epoxy resin.When the amine-modified epoxy resin for the different amine value hydroxyl values being used in combination of two or more, it is based on used amine The average amine value and average hydroxyl value that the mass ratio of modified epoxy calculates are preferably above-mentioned numberical range.In addition, as simultaneously The modified ring of the amine that amine-modified epoxy resin (A), preferably amine value are 20 ~ 50mgKOH/g and hydroxyl value is 50 ~ 300mgKOH/g The amine-modified epoxy resin that oxygen resin is 50 ~ 200mgKOH/g with amine value and hydroxyl value is 200 ~ 500mgKOH/g is used in combination.If Using such combination, there is the core portion due to lotion to become more hydrophobic, shell portion becomes hydrophilic, thus can assign excellent corrosion-resistant The advantages of property.

It is noted that in the cation electric deposition paint composition of this specification, as needed in addition to amine modified epoxy Resin (A) can also contain amino-containing polyester resin of amino-containing acrylic resin etc..

Curing agent (B)

The curing agent (B) contained in cation electric deposition paint composition of the invention be in a heated condition with amine modified epoxy The film that resin (A) carries out curing reaction forms resin.As curing agent (B), it is preferable to use melamine resin or sealing end are different Cyanate curing agent.The applicable blocked isocyanate curing agent for making curing agent (B) can be by by polyisocyanates end-capping reagent Sealing end is to prepare.

As the example of polyisocyanates, hexamethylene diisocyanate (including tripolymer) tetramethylene two can be enumerated The aliphatic diisocyanates such as isocyanates trimethyl hexamethylene diisocyanate；Isophorone diisocyanate 4,4 '- The ester ring types polyisocyanates such as di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate)；4,4 '-methyl diphenylene diisocyanate toluene two are different The aromatic diisocyanates such as cyanate benzene dimethylene diisocyanate；Modifier (the carbamic acid of these diisocyanate Carboxylate ( Compound) carbodiimide urea diketone uretonimine biuret and/or isocyanurate-modified object etc.).

As the example of end-capping reagent, n- butanol n- hexanol 2-Ethylhexyl Alcohol laruyl alcohol phenol methanol is preferably used Alkyl (or aromatic series) alcohols of the unitary such as (phenol carbinol) methyl phenyl carbinol；Ethylene glycol mono hexyl ether second two The dioxanes such as alcohol single 2-ethyl hexyl ether；Two end of the polyether-types such as polyethylene glycol polypropylene glycol polytetramethylene ether diol phenol End type glycols；The glycols such as ethylene glycol propylene glycol 1,4- butanediol and oxalic acid succinic acid adipic acid suberic acid decanedioic acid The two end polyalcohols of polyester-type that equal omega-dicarboxylic acids obtain；The phenols such as p- t- butylphenol cresols；Dimethyl ketone isonitrosomethyl The oximes such as ethyl ketoxime methyl isobutyl ketoxime methyl amyl ketoxime cyclohexanone oxime；With with epsilon-caprolactams γ-Ding Nei acyl Amine is the lactams of representative.

The sealing end rate of blocked isocyanate curing agent is preferably 100%.There is the storage of electrodeposition coating composition as a result, The advantages of having good stability.

Blocked isocyanate curing agent is preferably used in combination to be prepared and by aliphatic diisocyanate with blocking agent Curing agent with by by aromatic diisocyanate with blocking agent and the curing agent for preparing.

The primary amine preferential reaction of blocked isocyanate curing agent and amine-modified epoxy resin (A), further reacts with hydroxyl And solidify.

As melamine resin, it can be mentioned, for example the partially or completely methylolations that melamine is reacted with formaldehyde The melamine resin portion that is partially or completely etherified the methylol of methylolated melamine resin with alcohol component Point or alkyl ether type melamine resin contains the melamine resin and these mixed type melamine of imino group completely Polyimide resin.Here, such as methylated melamine resins butylation trimerization can be enumerated as alkyl ether type melamine resin Melamine resin methyl/butyl mixed alkyl type melamine resin etc..

It, can will be in metal-cured dose of organic curing agent silane coupling agent selected from phenolic resin etc. as curing agent At least one curing agent etc. is used in combination with above-mentioned melamine resin and/or blocked isocyanate curing agent.

3rd group element compound (C)

Cation electric deposition paint composition of the invention contains the 3rd group element compound (C).Pass through cation electrodeposition coating Contain the 3rd group element compound (C) in composition, obtains the excellent cured electrodeposition film of rust-preventing characteristic.It is preferred that the 3rd race's element Closing object (C) is the mixture lanthanum hydroxide selected from lanthana lanthanum hydroxide neodymia neodymium hydroxide lanthana and organic acid With a kind or a kind in the mixture of the mixture neodymia of organic acid and the mixture neodymium hydroxide of organic acid and organic acid More than.More preferable above-mentioned 3rd group element compound (C) is lanthanum compound, further preferred above-mentioned 3rd group element compound (C) For a kind in the mixture of mixture lanthanum hydroxide and organic acid selected from lanthana lanthanum hydroxide lanthana and organic acid Or a kind or more.

It is used in lanthana lanthanum hydroxide neodymia and neodymium hydroxide at least as the 3rd group element compound (C) At a kind, these the 3rd group element compounds can be powder morphology.When 3rd group element compound is powder morphology, preferably it is flat Equal partial size is 0.01 ~ 10 μm, more preferably 0.05 ~ 2 μm.In this specification, average grain diameter is volume average particle size D50, is referred to Using laser-Doppler formula Particle Size Analyzer (Ji Zhuan society manufacture,UPA150), dispersion is handed over ion Water is changed to dilute so that the signal level suitably value of measurement.

As the 3rd group element compound (C), when using the mixture of lanthana and/or lanthanum hydroxide and organic acid, can lead to It crosses and is pre-mixed lanthana and/or lanthanum hydroxide and organic acid to prepare mixture.As organic acid, preferably using for example 1 kind or a kind or more the compound in hydroxy monocarboxylic acids and sulfonic acid.

As hydroxycarboxylic acid, it can be mentioned, for example compounds below:

The monohydroxy monocarboxylic acid especially aliphatic monohydroxy groups list of the total carbon atom number 2 ~ 5 preferably 2 ~ 4 of lactic glycolic acid etc. Carboxylic acid；

The dihydroxy monocarboxylate of the total carbon atom number 3 ~ 7 preferably 3 ~ 6 of dihydromethyl propionic acid (DMPA) glyceric acid etc. is especially Aliphatic dihydroxy monocarboxylate.

Sulfonic acid is organic sulfonic acid, and it can be mentioned, for example the alkyl sulphurs of the total carbon atom numbers such as methanesulfonic acid ethanesulfonic acid 1 ~ 5 preferably 1 ~ 3 Acid.

More preferable organic acid is a kind or a kind or more in lactic acid dihydromethyl propionic acid and methanesulfonic acid.

The use form of organic acid is not particularly limited, and it can be mentioned, for example solid forms liquid forms to be dissolved in solvent Solution morphology (especially aqueous solution).It is preferred that organic acid is used in the form of aqueous solution.As the water that can be used for organic acid The solvent of the preparation of solution can enumerate the water of ion exchange water pure water distilled water etc. and with water water as main component Property solvent etc..Aqueous solvent as needed can also (such as alcohol ester ketone etc. be water-soluble or water is mixed containing organic solvent in addition to water Conjunction property organic solvent etc.).

When the mixture of previously prepared lanthana and/or lanthanum hydroxide and organic acid, lanthanum in lanthana and/or lanthanum hydroxide Molal quantity and the ratio of molal quantity of organic acid be preferably lanthanum: in the range of organic acid=1:0.3 ~ 1:2.7.Lanthanum is to become trivalent The rare earth element of cation.Also, the applicable hydroxy monocarboxylic acids for making organic acid and sulfonic acid are the acid of 1 valence.Therefore, lanthanum rubs The ratio of the molal quantity of that number and organic acid is lanthanum: when in the range of organic acid=1:0.3 ~ 1:2.7, relative to by lanthanum member The total valence mumber (i.e. molal quantity × 3 of metallic element) for the cation that element obtains, by the total valence mumber for the anion that organic acid obtains (molal quantity of organic acid) is insufficient state.It, can be with above-mentioned ratio using lanthana and/or lanthanum hydroxide and organic acid Preparation can provide that edge part rustless property is especially excellent, and the cationic electrodeposition of the cured coating film with excellent appearance of film Coating composition.The ratio of more preferable above-mentioned molal quantity is lanthanum: in the range of organic acid=1:0.6 ~ 1:2.4, further preferably Lanthanum: in the range of organic acid=1:0.9 ~ 1:2.1.

Relative to the resin solid content of cation electric deposition paint composition, cation electrodeposition coating group of the invention It is the amount as 0.01 ~ 2 mass % that the content for closing the 3rd group element compound (C) contained in object, which is preferably scaled metallic element, The amount for more preferably becoming 0.05 ~ 1.5 mass %, further preferably becomes the amount of 0.05 ~ 1 mass %.3rd group element compound (C) Amount when being unsatisfactory for above range, it is possible to cannot get excellent rustless property.In addition, the content of the 3rd group element compound (C) When more than above range, a possibility that appearance of film of the cured electrodeposition film having is deteriorated.

In this specification, " resin solid content of cation electric deposition paint composition " refers to that film forms consolidating for resin Body composition quality.Specifically, referring to the total of the quality of the resin solid content of amine-modified epoxy resin (A) and curing agent (B) Amount.

" being scaled metallic element " refers to that the content of the 3rd group element compound multiplied by metallic element conversion coefficient (is to be used for 3rd group element compound amount is scaled to the coefficient of metallic element amount, specifically, referring to will be in the 3rd group element compound The value that the atomic weight of 3rd race's element is obtained divided by the molecular weight of the 3rd group element compound), find out the metallic element amount of target.Example Such as, the 3rd group element compound (C) is lanthana (La₂O₃Molecular weight 325.8) when, for the electricity containing 0.1 mass % lanthana The metallic element conversion content of lanthanum in electrodeposition coating compositions, passes through 0.1 mass % × ((138.9 × 2) ÷ 325.8) meter It calculates, calculates as 0.0853 mass %.

When the content ratio of 3rd group element compound (C) is unsatisfactory for above range, it is possible to cannot get sufficient edge part Rustless property.In addition, having the 3rd group element compound (C) when the content ratio of the 3rd group element compound (C) is more than above range Dissolubility and it is uniformly dispersed reduce cation electric deposition paint composition storage stability reduce a possibility that.

Cation or non-ionic resin (D)

Cation electric deposition paint composition of the invention contains cation or non-ionic resin (D).Pass through cationic electrodeposition Containing above-mentioned 3rd group element compound (C) and both above-mentioned cation or non-ionic resin (D) in coating composition, obtain The excellent cation electric deposition paint composition of edge part rust-preventing characteristic.

In the present invention, the number-average molecular weight with above-mentioned cation or non-ionic resin (D) is that 10,000 the above are conditions.It is logical The number-average molecular weight for crossing above-mentioned cation or non-ionic resin (D) is 10,000 or more, such as is had even if 25 ~ 50 μm of film thickness of formation Higher film thickness cured electrodeposition film when, also ensure that the advantage of good corrosion resistance etc..It is preferred that the above-mentioned equal molecule of number In the range of amount is 10,000 ~ 20,000,000.

As above-mentioned cation or non-ionic resin (D), it can be mentioned, for example be selected from polyacrylamide resin chitosan resin With a kind or a kind or more in amine-modified epoxy resin.It is preferred that above-mentioned cation or non-ionic resin (D) are selected from polyacrylamide 1 kind or a kind or more resin in polyimide resin and amine-modified epoxy resin.

In this specification, " polyacrylamide resin " refers to the resin in polymer backbone containing acrylamide unit.Make For the specific example of the polyacrylamide resin of mentioned component (D), cationic polyacrylamide resin and nonionic can be enumerated Property polyacrylamide resin.Above-mentioned polyacrylamide resin can be for example, by that will contain the free radical polymerization of (methyl) acrylamide Property monomer carry out polymerization reaction and prepare.Above-mentioned free radical polymerization monomer as needed can containing (methyl) acrylamide and Other free radical polymerization monomers.In this specification, (methyl) acrylamide refers to acrylamide and/or Methacrylamide.

For example, in the preparation of cationic polyacrylamide resin, (the first that contains in above-mentioned free radical polymerization monomer Base) amount of acrylamide is preferably 70 mass % or more.Such as in the preparation of nonionic polyacrylamides resin, it is above-mentioned from Amount by (methyl) acrylamide contained in base polymerizable monomer is preferably 25 mass % or more.

As above-mentioned other free-radical polymerized property monomers, it can be mentioned, for example cationic vinyl monomer anionic property second Alkenyl monomer N- replaces (methyl) acrylamide (methyl) sodium allylsulfonate and vinyl monomer etc..

As above-mentioned cationic vinyl monomer, it can be mentioned, for example allylamine N, N- dimethyl aminoethyls (methyl) Acrylate N, N- diethylamino ethyl (methyl) acrylate N, N- dimethylaminopropyl (methyl) acrylamide N, The salt etc. of N- diethyl amino propyl (methyl) acrylamide and they.

As above-mentioned anionic property vinyl monomer, it can be mentioned, for example the monocarboxylic acids such as (methyl) acrylic acid crotonic acid, Malaysias The dicarboxylic acids such as furmaric acid itaconic acid muconic acid citraconic acid, vinyl sulfonic acid styrene sulfonic acid 2- acrylamide -2- first The organic sulfonic acids such as base propane sulfonic acid；Or sodium salt sylvite of these various organic acids etc..

N- replaces (methyl) acrylamide to replace (methyl) third if it is the N- other than above-mentioned cationic vinyl monomer Acrylamide is not particularly limited, and well known substance can be used, it can be mentioned, for example N, N- dimethyl (methyl) acrylamide N, N- diethyl (methyl) acrylamide N, N- diisopropyl (methyl) acrylamide N- methyl (methyl) acrylamide N- ethyl (methyl) acrylamide N- isopropyl (methyl) acrylamide N-t- butyl (methyl) acrylamide etc..

As vinyl monomer, the monomer other than above-mentioned monomer, such as (methyl) methyl acrylate (methyl) third can be enumerated The alkyl-acrylates of olefin(e) acid ethyl ester (methyl) butyl acrylate etc.；The allylic monomers containing allyl such as allyl alcohol Class；(methyl) acrylonitrile；The bisacrylamide system of di-2-ethylhexylphosphine oxide (methyl) acrylamide ethylenebis (methyl) acrylamide etc. Monomer；The diacrylate monomer of ethylene glycol two (methyl) acrylate diethylene glycol (deg) two (methyl) acrylate etc.；Two allyls Amine divinylbenzene；Four hydroxyl first of 1,3,5- triacryl hexahydro-S- triazine Triallyl isocyanurate triallylamine Polyfunctional vinyls monomer such as methylmethane tetraacrylate etc..

Polyacrylamide resin can be by the way that the free radical polymerization monomer for containing (methyl) acrylamide for example to polymerize In the presence of initiator (peroxide system of azo system oxidation-reduction type etc.), in the solvent of water and/or organic solvent etc. into Row polymerization reaction and prepare.Above-mentioned polymerization temperature can suitably be selected according to type of polymerization initiator etc., for example, can for 50 ~ 200 DEG C, more preferably 90 ~ 160 DEG C.Polymerization reaction time for example can be 0.5 ~ 12 hour.Further, it is possible to use modified poly- third Acrylamide resin, the modified polyacrylamide resin are to have the polyacrylamide resin obtained by above-mentioned polymerization reaction What some functional group's (such as acrylamido anionic property base etc.) reactions or neutralization obtained.

As polyacrylamide resin, commercially available product can be used.As commercially available product, it can be mentioned, for example MT Company's manufactureSerial (nonionic polyacrylamides resin)Serial (nonionic polyacrylamide Polyimide resin)Serial (cationic polyacrylamide resin)Company's manufactureSeries (cationic polyacrylamide resin) N serial (nonionic polyacrylamides resin) etc..

Above-mentioned polyacrylamide resin is more preferably cationic polyacrylamide resin.Because of cationic polyacrylamide Polyimide resin has the interaction force that resin is formed with above-mentioned film.Cationic polyamide can be for example, by by (methyl) Acrylamide and above-mentioned cationic vinyl monomer and/or its derivative are copolymerized and prepare.Above-mentioned cationic vinyl list In body, such as N, N- dimethyl aminoethyl (methyl) acrylate etc. can be suitably used.As said derivative, can enumerate Such as above-mentioned cationic vinyl monomer chloromethanes quaternary ammonium salt () etc..

As cationic polyamide, strong cation polyacrylamide resin is more preferably used.Strong cation Polyacrylamide resin refers to the higher resin of mole ratio cationic present in polyacrylamide resin.As it is strong sun from Sub- property polyacrylamide resin, it can be mentioned, for example the cationic polyacrylamide resins that cationic degree is 1.0meq/g or more.

When using polyacrylamide resin as ingredient (D), preferred number average molecular weight 100,000 ~ 20,000,000 In range, in the range of more preferably 1,000,000 ~ 20,000,000.

The number-average molecular weight of the ingredients such as polyacrylamide resin (D) can be measured for example, by GPC method.

When using polyacrylamide resin as ingredient (D), what is contained in cation electric deposition paint composition is above-mentioned poly- Resin solid content 100 mass parts of the amount of acrylamide resin relative to above-mentioned amine-modified epoxy resin (A) and curing agent (B) Preferably 0.001 ~ 1 mass parts.When the amount of polyacrylamide resin is less than 0.001 mass parts, it is possible to cannot get polyacrylamide The sufficient edge part rust-preventing characteristic improvement effect of the addition bring of polyimide resin.In addition, the amount of polyacrylamide resin is more than 1 mass When part, the appearance of film of obtained cured electrodeposition film is possible to be deteriorated.

It is that 10,000 the above are conditions using the number-average molecular weight of the amine-modified epoxy resin as ingredient (D).The equal molecule of number The polyphenol that the amine-modified epoxy resin that amount is 10,000 or more can be 10,000 or more by using number-average molecular weight contracts more Water glycerol type epoxy resin is prepared as with above-mentioned amine-modified epoxy resin (A).

When using amine-modified epoxy resin as ingredient (D), number-average molecular weight is preferably 10,000 ~ 5,000,000 model In enclosing, in the range of more preferably 10,000 ~ 2,000,000.

When as ingredient (D) using above-mentioned amine-modified epoxy resin, contain in cation electric deposition paint composition upper State resin solid content 100 matter of the amount of amine-modified epoxy resin relative to above-mentioned amine-modified epoxy resin (A) and curing agent (B) Measuring part is preferably 1 ~ 20 mass parts, more preferably 5 ~ 15 mass parts.When the amount of above-mentioned amine-modified epoxy resin is less than 1 mass parts, It may not be obtained the sufficient edge part rust-preventing characteristic improvement effect of addition bring of above-mentioned amine-modified epoxy resin.On in addition, When stating the amount of amine-modified epoxy resin more than 20 mass parts, the appearance of film of obtained cured electrodeposition film is possible to become Difference.

The chitosan resin that chitosan resin as ingredient (D) is 10,000 or more if it is number-average molecular weight, then may be used It uses without particular limitation.Chitosan resin can be for example, by will be by the crust of the extractions such as the crustacean crust such as crab or shrimp Matter carries out deacetylated processing, prepares chitosan, which is processed into resin and is prepared.

Commercially available product can be used in chitosan resin as ingredient (D).As commercially available product, it can be mentioned, for example(Dainichiseika Color Chem's manufacture) etc..

When using chitosan resin as ingredient (D), the range of preferred number average molecular weight 100,000 ~ 5,000,000 It is interior, in the range of more preferably 100,000 ~ 2,000,000.

The chitosan resin contained when using chitosan resin as ingredient (D), in cation electric deposition paint composition Amount relative to 100 mass parts of resin solid content of above-mentioned amine-modified epoxy resin (A) and curing agent (B) be preferably 0.01 ~ 10 mass parts, more preferably 0.05 ~ 5 mass parts.When the amount of chitosan resin is less than 0.01 mass parts, it is possible to it is poly- to cannot get shell The sufficient edge part rust-preventing characteristic improvement effect of the addition bring of glucoresin.In addition, the amount of chitosan resin is more than 10 mass parts When, the appearance of film of obtained cured electrodeposition film is possible to be deteriorated.

As ingredient (D), a kind in above-mentioned resin can be used, it can also be by 2 kinds or two or more is used in combination.

In the present invention, by cation electric deposition paint composition contain above-mentioned 3rd group element compound (C) and on Cation or non-ionic resin (D) are stated, excellent edge part rust-preventing characteristic can be obtained.It is without intending to be bound by theory, but it is believed that this be by In by, containing above-mentioned cation or non-ionic resin (D), will be precipitated on coated article in cation electric deposition paint composition The process that is heating and curing of electrodeposition coating in, can control and shunk caused by heating, it is heavy that the electricity being precipitated in edge part can be kept here Product film and the 3rd group element compound (C) of precipitation.When the heating of electrodeposition coating is precipitated, while generating hot-fluid, generate With the contraction of curing reaction.The contraction especially becomes larger when forming thick film.Cation electrodeposition coating group in the present invention Electrodeposition coating and the 3rd group element compound (C) of precipitation can be kept here due to having the function of by closing object, be applicable to In being arranged such as the case where 25 ~ 50 μm of film thickness of high film thickness cured electrodeposition film.

In the present invention, even if contain such as carbon black as pigment in cation electric deposition paint composition, by containing There are above-mentioned cation or non-ionic resin (D), the cured electrodeposition film with good rust-preventing characteristic can be formed by also having. Carbon black is black pigment, is conductive pigment.Therefore, when containing carbon black in cation electric deposition paint composition, In the electrodeposition coating process that electrodeposition coating is precipitated, by the precipitation of conductive carbon black, the 3rd race member is generated sometimes The position that the precipitation of plain compound (C) is obstructed.Even if in this case, by cation electric deposition paint composition Containing above-mentioned cation or non-ionic resin (D), it is being heating and curing in process, as noted previously, as electrodeposition coating can be kept here And the 3rd group element compound (C) being precipitated, therefore obtain excellent rust-preventing characteristic.

Pigment dispersion paste material

Cation electric deposition paint composition of the invention can contain pigment dispersion paste material as needed.Pigment dispersion paste material is The ingredient optionally contained in electrodeposition coating composition, typically contains pigment dispersing resin and pigment.

Pigment dispersing resin

Pigment dispersing resin is the resin for dispersing pigment, dispersible to use in an aqueous medium.Disperse to set as pigment Rouge can be used and have at least one kind of or a kind or more of the modified epoxy etc. in the tertiary sulfonium base of quaternary ammonium group and primary amino group There is the pigment dispersing resin of cation group.As aqueous medium, using ion exchange water or contain the hydrophilies such as a small amount of alcohols The water etc. of solvent.

Pigment

Pigment is the pigment generally used in electrodeposition coating composition.As pigment, it can be mentioned, for example usually used inorganic Pigment and organic pigment, such as coloring pigment as titanium white (titanium dioxide) carbon black and iron oxide red；Kaolin talcum silicon Extender pigment as sour aluminium carbonic acid calcium mica and clay；Ferric phosphate aluminum phosphate calcium phosphate aluminium triphosphate and phosphomolybdic acid Rust resisting pigment as aluminium aluminium zinc phosphomolybdate etc..

The manufacture of pigment dispersion paste material

Pigment dispersing resin and pigment are mixed and are prepared by pigment dispersion paste material.Pigment dispersing resin in pigment dispersion paste material Content is not particularly limited, and is calculated as 20 ~ 100 mass for example, can be used relative to 100 mass parts of pigment with resin solid content ratio The amount of part.

The solid content of preferred pigments dispersion thickener is 40 ~ 70 mass % relative to pigment dispersion paste material total amount, especially 50 ~ 60 mass %.

In this specification, " solid component of pigment dispersion paste material " refers to the ingredient contained in pigment dispersion paste material, passes through Removing solvent becomes the quality of solid and remaining all the components.Specifically, referring to the pigment contained in pigment dispersion paste material The total amount of the quality of dispersion resin and pigment and the other solid components being added as needed.

Bismuth compound

Cation electric deposition paint composition of the invention can contain bismuth compound as needed.Bismuth compound is containing bismuth gold The compound of category, it can be mentioned, for example bismuth oxide bismuth hydroxide bismuth nitrate or their mixtures.Preferred bismuth compound is choosing It is at least one kind of in autoxidation bismuth and bismuth hydroxide.

When using bismuth compound, the amount of the bismuth compound contained in the electrodeposition coating composition in the present invention is relative to electricity It is preferably 0.05 ~ 1.0 mass % that the resin solid content contained in electrodeposition coating compositions, which is scaled metallic element,.Pass through bismuth The amount for closing object is above range, and resin component can solidify well, and the storage stability of cation electric deposition paint composition It can maintain good.The content for being scaled metallic element of bismuth compound can be asked in the same manner as above-mentioned metallic element conversion content Out.

It is preferred that the average grain diameter of above-mentioned bismuth compound is 1 ~ 500nm.It is above range by average grain diameter, has performance good Curability etc. advantage.

When using bismuth compound, it can be used with the state being pre-mixed with sour component.Such as it can be by bismuth compound and acid Ingredient is pre-mixed, and obtained mixture is mixed in the preparation of pigment dispersion paste material, is thus prepared containing bismuth compound Pigment dispersion paste material.As the preparation method of the pigment dispersion paste material containing bismuth compound, it can be mentioned, for example will be pre-mixed The bismuth mixture that bismuth compound and sour component (such as above-mentioned organic acid etc.) obtain mixes with resin component, then hybrid pigment Preparation method etc..In the preparation method, as resin component, it can be used usually used in such as preparation of pigment dispersion paste material The mixture etc. of the above-mentioned amine-modified epoxy resin of pigment dispersing resin (A) and curing agent (B).These resin components can only make With a kind, it also can be used together 2 kinds.

In paint field, organotin catalysts are generally used as curing catalysts.But organotin catalysts are by close It is from now on using the catalyst that may be restricted from the point of view of the environmental Kuznets Curves trend of phase.The curability of above-mentioned bismuth compound is excellent, Therefore it can be used as the alternative catalysts of the organotin catalysts used generally as curing catalysts in paint field.Therefore, By using above-mentioned bismuth compound, there is the advantages of cation electric deposition paint composition that carrying capacity of environment reduction can be provided.

The manufacture of cation electric deposition paint composition

Electrodeposition coating composition of the invention can be by that will contain the lotion of amine-modified epoxy resin (A) and curing agent (B) 3 group element compounds (C) cation or non-ionic resin (D) and pigment dispersion paste material as needed and addition drug etc. are mixed It closes and prepares.

In the preparation of electrodeposition coating composition, it can be formed point by neutralizing amine-modified epoxy resin (A) with neutralizing acid Dissipate the lotion that property improves.Neutralizing acid as the neutralization for amine-modified epoxy resin (A) is, it is preferable to use arboxylic acid lactic acid Equal organic acids.When using above-mentioned acid as the neutralizing acid that amine-modified epoxy resin (A) is neutralized and dispersed, have due to degree of dissociation height And the advantage that spreading is excellent.

Used antacid amount relative to contain amine-modified epoxy resin (A) curing agent (B) and painting as needed The resin solid content 100g of film formation resin is preferably the range of 10 ~ 25mg equivalent.Above-mentioned lower limit is more preferably 15mg equivalent, The more preferable above-mentioned upper limit is 20mg equivalent.It is 10mg equivalent or more by antacid amount, it is abundant to the compatibility of water, in water It is well dispersed.It on the other hand, is 25mg equivalent hereinafter, electricity required for being precipitated is suitable by antacid amount, coating is solid The precipitation spreading of body ingredient is good.

The amount of curing agent (B) needs for for the brothers hydroxy amino when solidifying and in amine-modified epoxy resin (A) Full amount for good cured coating film is obtained Deng the functional group reactions containing reactive hydrogen.The amount of preferred curing agent (B) with The solid component mass ratio (amine-modified epoxy resin (A)/curing agent (B)) of amine-modified epoxy resin (A) and curing agent (B) indicate For 90/10 ~ 50/50 more preferable 80/20 ~ 65/35 range.Pass through the solid of amine-modified epoxy resin (A) and curing agent (B) The mobility and curing rate of the electrodeposition coating being precipitated is adjusted in the adjusting of composition quality ratio.

Electrodeposition coating composition can be by being added resin emulsion pigment dispersion paste material and the 3rd group element compound (C) cation or non-ionic resin (D) and pigment dispersion paste material as needed etc. are mixed and are prepared, and the resin emulsion is Amine-modified epoxy resin (A) curing agent (B) and other films as needed are formed resin component neutralizing acid to disperse to obtain 's.It is noted that the 3rd group element compound (C) adds after dispersion thickener can be made together with pigment.

In this specification, " solid component of electrodeposition coating composition " refer to contain in electrodeposition coating composition at Point, become the quality of the remaining all the components of solid by removing solvent.Specifically, referring in electrodeposition coating composition Amine-modified epoxy resin (A) curing agent (B) the 3rd group element compound (C) pigment dispersing resin pigment for containing and according to Need the total amount of the quality of other solid components to be added.

The solid content of cation electric deposition paint composition of the invention is relative to electrodeposition coating composition total amount Preferably 1 ~ 30 mass %.When the solid content of electrodeposition coating composition is less than 1 mass %, quantitative change is precipitated in electrodeposition coating It is few, it is possible to be difficult to ensure sufficient corrosion resistance.In addition, the solid content of electrodeposition coating composition is more than 30 mass % When, spreading or coating appearance are possible to be deteriorated.

The preferred pH of cation electric deposition paint composition of the invention is 4.5 ~ 7.The pH of electrodeposition coating composition is less than When 4.5, sour amount present in cation electric deposition paint composition is excessive, and appearance of film or painting operation are possible to become Difference.On the other hand, when pH is more than 7, the filterability of electrodeposition coating composition is reduced, and the horizontal appearance of cured electrodeposition film has When reduce.The pH of electrodeposition coating composition can be set by adjusting the additive amount etc. of used antacid amount free acid In above range.Above-mentioned pH is more preferably 5 ~ 7.

The commercially available pH meter with temperature compensation function can be used to measure for the pH of electrodeposition coating composition.

Preferably with respect to electrodeposition coating composition solid component 100g acid milliequivalent (MEQ (A)) be 40 ~ 120.It is noted that the milliequivalent (MEQ (A)) of the acid of the resin solid content 100g relative to electrodeposition coating composition It can be adjusted by neutralizing acid amount and the amount of free acid.

Here, MEQ (A) is the abbreviation of mg equivalent (acid), it is all of the every 100g of solid component of coating The mg equivalent of acid adds up to.The MEQ (A) can claim the solid component about 10g of electrodeposition coating composition by essence, be dissolved in about After the solvent (THF: tetrahydrofuran) of 50ml, constant-current titration is carried out using the NaOH solution of 1/10N, to electrodeposition coating composition In contain acid amount quantified and measured.

Cation electric deposition paint composition of the invention can add as needed containing what is generally used in paint field Add agent, such as ethylene glycol monobutyl ether ethylene glycol mono hexyl ether ethylene glycol list ethylhexyl ether glycol monobutyl ether dipropyl The drying of the organic solvents such as glycol single-butyl ether propylene glycol list phenyl ether prevents the surfactants acrylic acid tree such as Antifoam Agent Inorganic inhibitors such as the viscosity modifiers anticrater agent vanadic salts copper and iron manganese tachydrite such as fat granule etc..In addition, in addition to this A bit, according to purpose can also be compounded well known chelating auxiliary agent () buffer lubricant stress moderator light Damp agent semi-glossy agent antioxidant and ultraviolet absorbing agent etc..These additives can when manufacturing resin emulsion the 2nd mixing Shi Tianjia, can also make paints disperse thickener when addition, can also be when resin emulsion and pigment dispersion paste material be mixed Or it is added after mixing.

Cation electric deposition paint composition of the invention can also contain other than above-mentioned amine-modified epoxy resin (A) Other films form resin component.Resin component is formed as other films, it can be mentioned, for example acrylic resin polyester trees Rouge polyurethane resin butadiene-based resin phenolic resin xylene resin etc..Contain in electrodeposition coating composition its Its film forms the preferred phenolic resin xylene resin of resin component.As phenolic resin xylene resin, example can be enumerated Such as with the xylene resin of 2 or more 10 aromatic rings below.

In the present invention, the precipitation electrodeposition coating of cation electric deposition paint composition is preferred in 105 DEG C of painting film viscosity For 10Pa s or less.For being precipitated electrodeposition coating, 105 DEG C of temperature can be described as painting film resin that electrodeposition coating contains at Point curing reaction to start before temperature.105 DEG C of painting film viscosity of the electrodeposition coating under the conditions of temperature in this way For 10Pa s hereinafter, even if the ingredient (D) containing high molecular weight, the flowing of electrodeposition coating caused by heating is also ensured that, it can To avoid the membrane thickness unevenness of cured electrodeposition film.The lower limit value of 105 DEG C of painting film viscosity is not particularly limited, such as excellent It is selected as 1Pa s, more preferably 5Pa s.

The measurement of 105 DEG C of painting film viscosity can be carried out according to such as JIS K7244.To illustrate that JIS K7244 is pair It should be in the Japanese Industrial Specifications of ISO 6721.Precipitation electrodeposition coating specifically can be as steps described below in 105 DEG C of painting film viscosity Measurement.Firstly, carrying out 180 seconds electrodeposition coatings to coated article, film thickness is made to reach about 15 μm, forms electrodeposition coating, Jiang Qishui It washes, removes the electrodeposition coating composition redundantly adhered to.Then, the extra moisture for being attached to electrodeposition coating surface is removed Afterwards, it does not dry, removes film immediately, prepare sample.By using measurement of dynamic viscoelasticity device to the sample obtained in this way into Row viscosimetric analysis can measure the painting film viscosity at 105 DEG C.

In the present invention, the precipitation electrodeposition coating of cation electric deposition paint composition is preferred in 105 DEG C of standing viscosity For 200 ~ 5000Pa s, more preferably 1000 ~ 5000Pa s.Here, 105 DEG C of standing viscosity can be by setting shear velocity For d (gamma)/dt=0.011/ second, shear viscosity after being measured 300 seconds at 105 DEG C and find out.The survey of 105 DEG C of standing viscosity Surely it can be measured according to such as JIS 7244.It is noted that JIS 7244 corresponds to the Japanese Industrial Specifications of ISO 6721.

It is 200 ~ 5000Pa s by 105 DEG C of standing viscosity of above-mentioned precipitation electrodeposition coating, has to obtain excellent side The advantages of edge rust-preventing characteristic.It is thought that the process due to being heating and curing to the electrodeposition coating being precipitated on coated article In, the electrodeposition coating of edge part precipitation and the 3rd group element compound (C) of precipitation can be kept here.

In the present invention, cation electric deposition paint composition is preferably 10mPa s or less in 23 DEG C of viscosity of the coating.Sun from When the viscosity of the coating of sub- electrodeposition coating composition is in above range, it is possible to understand that even if cation electric deposition paint composition In containing above-mentioned cation or when non-ionic resin (D), have compared with the cation electric deposition paint composition previous with this field There is the viscosity of same degree.Thus, it is possible to definitely understand in cation electric deposition paint composition of the invention, do not pass through It improves the viscosity of the coating of electrodeposition coating composition merely to control the precipitation state of cured electrodeposition film, but passes through consideration The effect for each ingredient that electrodeposition coating composition contains, control cured electrodeposition film formed in each ingredient behavior, thus Reach excellent rust-preventing characteristic.

Brookfield viscometer (such as TOKIMEC company can be used in 23 DEG C of viscosity of the coating in cation electric deposition paint composition Manufacture), it is measured according to JIS K5601 and JIS K7117-1.It is noted that JIS K7117-1 corresponds to ISO's 2555 Japanese Industrial Specifications.

Cation electric deposition paint composition is not particularly limited in the lower limit value of 23 DEG C of viscosity of the coating, such as is preferably 1mPa s, more preferably 3mPa s.

Electrodeposition coating and electrodeposition coating are formed

Electrodeposition coating is carried out to coated article by using cation electric deposition paint composition of the invention, it is heavy that electricity can be formed Product film.In electrodeposition coating using cation electric deposition paint composition of the invention, using coated article as cathode, with Apply voltage between anode.Electrodeposition coating is precipitated on coated article as a result,.

What can be powered can be used various to be applied for the coated article of the cation electric deposition paint composition of the invention as coating Object.As workable coated article, it can be mentioned, for example the platings of cold-rolled steel sheet hot rolled steel plate stainless steel plated steel sheet fused zinc Plated steel sheet zinc-iron alloys system of steel plate Zn-Al alloy system plated steel sheet zinc-Magnesium Alloys plated steel sheet zinc-aluminium-magnesium is applied to close Plated steel sheet tin system of plated steel sheet aluminium-silicon alloys system of plated steel sheet aluminium system of gold system plated steel sheet etc..

In electrodeposition coating process, after impregnating coated article in electrodeposition coating composition, by the electricity for applying 50 ~ 450V Pressure carries out electrodeposition coating.Apply voltage to be less than 50V then electro-deposition may be insufficient, if it exceeds 450V, then appearance of film It is possible that being deteriorated.When electrodeposition coating, the bath temperature of coating composition is usually adjusted to 10 ~ 45 DEG C.

Difference due to difference of electrodeposition condition of alive time is applied, generally can be 2 ~ 5 minutes.

In electrodeposition coating using cation electric deposition paint composition of the invention, for the electrodeposition coating of precipitation Film thickness, pass through film thickness preferably 5 ~ 60 μm of more preferable 10 ~ 50 μm of the film thickness for the finally obtained electrodeposition coating that is heating and curing. The film thickness of electrodeposition coating is if it is less than 5 μm, then rust-preventing characteristic may be insufficient.

After the electrodeposition coating being precipitated as described above is washed as needed, for example, by 120 ~ 260 DEG C preferably 140 ~ 220 DEG C of heating can solidify for 10 ~ 30 minutes.Cured electrodeposition film is consequently formed.

By using cation electric deposition paint composition of the invention, have even if being set on the coated article with edge part When setting such as 25 ~ 50 μm of film thickness of high film thickness cured electrodeposition film, it is heavy to may also set up the excellent solidification electricity of edge part rust-preventing characteristic The advantages of product film.Cation electric deposition paint composition of the invention can keep electrodeposition coating and precipitation here due to having The function of 3rd group element compound (C), therefore the feelings of the high film thickness cured electrodeposition film at such as 25 ~ 50 μm of film thickness of setting It is also applicable in condition etc..

In this specification, the corrosion resistance evaluation of the cured electrodeposition film formed on the coated article with edge part is logical Salt spraytest (35 DEG C × 168 hours) based on JIS Z 2371 (2000) are spent to carry out.Such as 25 ~ 50 μm of film thickness of high film Thick cured electrodeposition film is in salt spraytest, the side of the cured electrodeposition film formed on the coated article with edge part Number occurs for getting rusty for edge finish department in the every 1cm in edge part²In to be, for example, less than 5/cm²When, it may be said that it is the corrosion resistant of edge part The excellent film of corrosion (rust-preventing characteristic).It is noted that JIS Z 2371 (2000) corresponds to the Japanese industry of ISO 9227 Specification.

Embodiment

The present invention is further illustrated by embodiment below, but the present invention is not limited to these.In embodiment " part " and " % " is quality criteria when being not particularly illustrated.

The manufacture of 1 pigment dispersing resin of Production Example

2-Ethylhexyl Alcohol half blocks the preparation of isophorone diisocyanate

Isophorone diisocyanate is added in the reaction vessel equipped with agitating device condenser pipe nitrogen ingress pipe and thermometer Tin dilaurate two is added after 39.1 parts of methyl iso-butyl ketone (MIBK) (MIBK) dilutions in 222.0 parts of (hereinafter referred to as IPDI) thereto 0.2 part of butyl tin.Then, after being warming up to 50 DEG C, 2-Ethylhexyl Alcohol was added dropwise in dry nitrogen atmosphere under stiring with 2 hours It 131.5 parts, obtains 2-Ethylhexyl Alcohol and partly blocks IPDI (90.0 mass % of solid component).

Quaternising agents ( ) preparation

87.2 part 75% of dimethylethanolamine, 117.6 parts of lactic acid aqueous solution and ethylene glycol list n- fourth are sequentially added into reaction vessel It 39.2 parts of base ether, is stirred 30 minutes at 65 DEG C, prepares quaternising agents.

The manufacture of pigment dispersing resin

By bisphenol A type epoxy resin (trade name: DER-331JCompany's manufacture) 710.0 parts and bisphenol-A 289.6 It in part addition reaction vessel, is reacted 1 hour in nitrogen atmosphere at 150 ~ 160 DEG C, after being then cooled to 120 DEG C, is added and adjusts in advance The 2-Ethylhexyl Alcohol of system partly blocks 498.8 parts of IPDI (MIBK solution).Reaction mixture is stirred 1 hour at 110 ~ 120 DEG C, is added Enter 463.4 parts of butyl ether of ethylene glycol list n-, mixture is cooled to 85 ~ 95 DEG C, adds 196.7 parts of quaternising agents modulated in advance. By reaction mixture be maintained at 85 ~ 95 DEG C reach 1 to acid value after, be added 964 parts of deionized water, obtain targeted pigment dispersion resin (50 mass % of solid component).

The manufacture of 2 amine-modified epoxy resin of Production Example (A)

92 parts of bisphenol A type epoxy resin (trade name DER-331J of methyl iso-butyl ketone (MIBK) are addedCompany's manufacture) Temperature in reaction vessel is held in 140 DEG C, reaction by 940 parts of 382 parts of bisphenol-A, 2 parts of dimethyl benzyl amine of 63 parts of octanoic acids After reaching 1110g/eq to epoxide equivalent, the temperature being cooled in reaction vessel reaches 120 DEG C.Then diethylenetriamines is added The mixture that 78 parts and 92 parts of diethanol amine of diketimine (methyl isobutyl ketone solution of 73 mass % of solid component), at 120 DEG C Reaction 1 hour, thus obtains aminated resin (cation-modified epoxy resin).The number-average molecular weight of the resin is 2,560 amine values It is 240mgKOH/g for 50mgKOH/g (being wherein 14mgKOH/g from the amine value of primary amine) hydroxyl value.

The manufacture of Production Example 3-1 blocked isocyanate curing agent (B-1)

By 1680 parts of hexamethylene diisocyanate (HDI) and MIBK732 parts of addition reaction vessels, it is heated to 60 DEG C.? 60 DEG C are dissolved in 1067 parts of obtained solution of MEK oxime for 346 parts of trimethylolpropane with dropwise addition in 2 hours thereto.Further exist After 75 DEG C are heated 4 hours, in IR spectroscopic assay, confirms that the absorption based on isocyanate group disappears, after letting cool, MIBK27 is added Part, obtain the blocked isocyanate curing agent (B-1) that solid component is 78%.Isocyanates base value is 252mgKOH/g.

The manufacture of Production Example 3-2 blocked isocyanate curing agent (B-2)

By 1340 parts of 4,4 '-methyl diphenylene diisocyanate and MIBK277 parts of addition reaction vessels, it is heated to 80 DEG C Afterwards, 80 DEG C with 2 hours be added dropwise by 226 parts of epsilon-caprolactams be dissolved in 944 parts of butyl cellosolve obtained in solution.Further After 100 DEG C are heated 4 hours, absorption of the confirmation based on isocyanate group disappears in IR spectrum measurement, after letting cool, is added MIBK349 parts, obtain blocked isocyanate curing agent (B-2) (80 mass % of solid component).Isocyanates base value is 251mgKOH/g。

The manufacture of 4 amine-modified epoxy resin lotion of Production Example

Sealing end obtained in 350 parts of (solid component) Production Example 3-1 of amine-modified epoxy resin obtained in Production Example 2 (A) is different 75 parts of blocked isocyanate curing agent (B-2) obtained in cyanate curing agent (B-1) 75 parts (solid components) and Production Example 3-2 (solid component) mixing, adds the mono- 2- ethylhexyl ether of ethylene glycol, makes relative to solid component 3% (15 parts).Then, it is added Formic acid neutralizes, and additive amount is the amount for being equivalent to resin neutralization ratio 40%, and ion exchange water is added, slowly dilutes, then under reduced pressure Methyl iso-butyl ketone (MIBK) is removed, so that solid component is reached 40%, obtains aminated resin lotion.

The manufacture of 5 high molecular weight amine-modified epoxy resin of Production Example (molecular weight 20,000)

139 parts of bisphenol A type epoxy resin (trade names: DER-331J of methyl iso-butyl ketone (MIBK) are addedCompany's manufacture) Temperature in reaction vessel is held in 140 DEG C, reaction to epoxide equivalent by 940 parts of 444 parts of bisphenol-A, 2 parts of dimethyl benzyl amines After reaching 1340g/eq, the temperature being cooled in reaction vessel is 120 DEG C.

Then 79 parts of diethylenetriamines diketimine (methyl isobutyl ketone solution that solid component is 73 mass %) is added With 53 parts of mixture of N- methylethanolamine (MMA), is reacted 1 hour at 120 DEG C, it is (cation-modified thus to obtain aminated resin Epoxy resin).

After being cooled to 90 DEG C, ion exchange water is added and acetic acid neutralizes, additive amount is to be equivalent to resin neutralization ratio 80% Amount, makes solid component 20%.

Then bisphenol A type epoxy resin (trade name: DER-331J is addedCompany's manufacture) 188 parts, reaction 60 DEG C × 3 hours.Methyl iso-butyl ketone (MIBK) is removed under reduced pressure, obtains the high molecular weight amine-modified epoxy resin of solid component 20% (molecular weight 20,000).

The molecular weight of above-mentioned high molecular weight amine-modified epoxy resin is number-average molecular weight.High molecular weight amine-modified epoxy resin Molecular weight (number-average molecular weight) measure according to the following steps.

By the way that after being dried under reduced pressure etc. and removing moisture by obtained high molecular weight amine-modified epoxy resin, use is with polystyrene Gel permeation chromatography (GPC) on the basis of standard sample measures under the following conditions.

Device: 2695 Separations Module of alliance

Column: east TSK gel ALPHA-M

Flow velocity: 0.05ml/min

Detector: 2414 Refractive Index Detector of alliance

Mobile phase: N, N '-dimethyl formamide

Standard sample: TSK STANDARD POLYSTYRENE (manufacture of eastern ソー company) A-500 A-2500 F-1 F-4 F- 20 F-80 F-700 1- hexane phenyls (manufacture of ア Le De リッチ company).

The manufacture of 6 high molecular weight amine-modified epoxy resin of Production Example (molecular weight 1,000,000)

139 parts of bisphenol A type epoxy resin (trade names: DER-331J of methyl iso-butyl ketone (MIBK) are addedCompany's manufacture) 940 Temperature in reaction vessel is remained 140 DEG C by part 444 parts of bisphenol-A, 2 parts of dimethyl benzyl amine, and reaction to epoxide equivalent reaches To after 1340g/eq, the temperature being cooled in reaction vessel is 120 DEG C.

Then bisphenol A type epoxy resin (trade name: DER-331J is addedCompany's manufacture) 188 parts, reaction 90 DEG C × 3 hours.Methyl iso-butyl ketone (MIBK) is removed under reduced pressure, and the high molecular weight amine-modified epoxy resin for obtaining solid component 20% (divides Son amount 100 is ten thousand).

The manufacture of 1 high molecular weight amine-modified epoxy resin (molecular weight 6000) of comparison manufacturing example

139 parts of bisphenol A type epoxy resin (trade names: DER-331J of methyl iso-butyl ketone (MIBK) are addedCompany's manufacture) Temperature in reaction vessel is held in 140 DEG C, reaction to epoxide equivalent by 940 parts of 444 parts of bisphenol-A, 2 parts of dimethyl benzyl amines After 1340g/eq, the temperature being cooled in reaction vessel is 120 DEG C.

Then, diethylenetriamines diketimine (methyl isobutyl ketone solution that solid component is 73 mass %) 79 is added Part and 53 parts of N- methylethanolamine (MMA) mixture, reacted 1 hour at 120 DEG C, thus obtaining aminated resin, (cation changes Property epoxy resin).

Then, bisphenol A type epoxy resin (trade name: DER-331J is addedCompany's manufacture) 188 parts, reaction 50 DEG C × 2 hours.Methyl iso-butyl ketone (MIBK) is removed under reduced pressure, and the high molecular weight amine-modified epoxy resin for obtaining solid component 20% (divides Son amount is 6000).

Embodiment 1

The preparation of cation electric deposition paint composition

To pigment dispersing resin (50 mass % of solid component) 60.0 obtained in addition Production Example 1 in 116.6 parts of ion exchange water Mass parts and 100 parts of lanthana, stirring, are made mixture, obtain oxygen at 40 DEG C using sand mill with 2000rpm stirring 1 hour Change lanthanum thickener.The solid component concentration of obtained lanthana thickener is 47 mass %.

In other containers, 5.1 parts of 50% lactic acid aqueous solution and bismuth oxide are stirred in 110.1 parts of ion exchange water 6.5 part.56.7 mass parts of pigment dispersing resin obtained in Production Example 1 are added thereto, at room temperature with 1000rpm stirring 1 Hour.Here, adding 7.1 part 10% of amine-modified epoxy resin lotion, 1.4 parts of aqueous tartaric acid solution obtained in Production Example 4 and stirring It mixes, then, adds 8 parts of 86.6 parts of Satintone (calcined kaolin) of carbon black as pigment, then, be added obtained above 15.3 parts of lanthana thickener, using sand mill at 40 DEG C with 2000rpm stirring 1 hour, obtaining solid component concentration is 47 mass % Pigment thickener.

It is added in 99.5 parts of ion exchange water as ingredient (D)N100S (nonionic polyacrylamides tree Rouge MTCompany manufactures number-average molecular weight: about 1,300 ten thousand) 0.5 part, at stirring at normal temperature 60 minutes, obtaining containing poly- third The preparation solution of acrylamide resin.

It then, will be to the above-mentioned preparations of addition in 250 parts of amine-modified epoxy resin lotion (solid component 40%) of Production Example 4 6 parts of preparation solution (solid component 0.5%) obtained substances as F2 lotion.Obtained F2 is used in following estimation of stability In addition lotion evaluates stability.

By the pigment thickener of 1539 parts of 1997 parts of ion exchange water above-mentioned F2 lotions and above-mentioned preparation in rustless steel container 464 parts 40 DEG C aging 16 hours, obtain cation electric deposition paint composition.

The formation (20 μm of cold-rolled steel sheet film thickness) of cured electrodeposition film (1)

Cold-rolled steel sheet (JIS G3141 SPCC-SD) is existedEC90 (JapanCompany manufacture) at 50 DEG C Dipping 2 minutes carries out ungrease treatment.Then, existGL1 (JapanCompany manufacture) in normal temperature dipping 30 seconds, then existEC3200 (JapanCompany manufactures zirconium chemical conversion treatment Agent) in 35 DEG C impregnate 2 minutes.Then, it is washed with deionized water.

The mono- 2- ethylhexyl ether of ethylene glycol of necessary amount is added into cation electric deposition paint composition obtained above (2-Ethyl Hexyl Glycol) makes 20 μm of film thickness of the electrodeposition coating after solidifying.

Then, it after burying steel plate completely in electrodeposition coating composition, immediately begins to apply voltage, to boost 30 Second, reach the condition kept after 180V 150 seconds and apply voltage, uncured electro-deposition painting is precipitated on coated article (cold-rolled steel sheet) Film.Obtained uncured electrodeposition coating is heating and curing 15 minutes at 160 DEG C, obtains the solidification electricity with 20 μm of film thickness The electrodeposition coating plate of electrodeposition coating film.

The formation (20 μm of the coated article film thickness with edge part) of cured electrodeposition film (2)

By coated article by cold-rolled steel sheet (JIS G3141 SPCC-SD) be changed to the dedicated replacing blade of L-type (LB10K:Strain Shi Hui company manufactures long 100mm wide 18mm thickness 0.5mm), in addition to this, with as described above the step of carry out ungrease treatment Surface treatment and chemical conversion treatment etc..

Then, cured electrodeposition film is arranged with the same step of the formation of above-mentioned cured electrodeposition film (1), having There is the cured electrodeposition film that 20 μm of film thickness are arranged on the coated article of edge part.

The formation (40 μm of the coated article film thickness with edge part) of cured electrodeposition film (3)

Application condition in electrodeposition coating is changed to the condition for boosting to 280V with 3 seconds, keeping 270 seconds in above-mentioned voltage Outside, with the step same as cured electrodeposition film (2), in the dedicated replacing blade of L-type as the coated article with edge part The upper cured electrodeposition film by adjusting 40 μm of temperature setting film thickness.

Embodiment 2

As ingredient (D), use is usedC535H (cationic polyacrylamide resin MTCompany Number-average molecular weight: about 800 4 parts of preparation solution containing ingredient (D) ten thousand) prepared is manufactured, in addition to this similarly to Example 1 Obtain cation electric deposition paint composition.

Using obtained cation electric deposition paint composition formed similarly to Example 1 cured electrodeposition film (1) ~ (3)。

Embodiment 3

Use is used as ingredient (D)C508 (strong cation polyacrylamide resin MTCompany It manufactures number-average molecular weight: other than about 800 4 parts of preparation solution containing ingredient (D) ten thousand) prepared, obtaining similarly to Example 1 Cation electric deposition paint composition.

Embodiment 4

As ingredient (D) using useC508LL (strong cation polyacrylamide resin MT Company manufactures number-average molecular weight: other than about 300 6 parts of preparation solution containing ingredient (D) ten thousand) prepared, similarly to Example 1 Obtain cation electric deposition paint composition.

Embodiment 5

It is prepared into 225 parts of amine-modified epoxy resin lotion (solid component 40%) additions, 50 parts of above-mentioned Production Examples 5 of Production Example 4 High molecular weight amine-modified epoxy resin (molecular weight: about 20,000) preparation solution, as F2 lotion.

By the pigment thickener of 1598 parts of 1938 parts of ion exchange water above-mentioned F2 lotions and above-mentioned preparation in rustless steel container 464 parts 40 DEG C aging 16 hours, prepare cation electric deposition paint composition.

Embodiment 6

As ingredient (D) using the high molecular weight amine-modified epoxy resin (molecular weight about 1,000,000) manufactured in Production Example 6, this is removed In addition, cation electric deposition paint composition is obtained similarly to Example 5.

Embodiment 7

It, will as ingredient (D)(industrial Zhu Shihui company manufacture of refining big day) is diluted to 1% obtained substance 10 250 parts of amine-modified epoxy resin lotion (solid component 40%) mixing of part and Production Example 4 are used as F2 lotion, in addition to this, with reality It applies example 5 and gets similarly cation electric deposition paint composition.

Embodiment 8

The preparation of cation electric deposition paint composition

To 5.3 parts of 50% lactic acid aqueous solution, 6.9 parts of bismuth oxide is added in 107.4 parts of ion exchange water, make the solid for dispersing thickener Constituent concentration is 47 mass %, is stirred at room temperature 1 hour.9.0 parts of 50% lactic acid aqueous solution and oxidation are further added thereto It 5.5 parts of lanthanum, is stirred at room temperature 1 hour and mixes.It is added obtained in Production Example 1 and (changes thereto for 60 parts of pigment dispersing resin Calculate the amount for resin solid content), at room temperature with 1000rpm stirring 1 hour.

Then 1.5 parts of 10% aqueous tartaric acid solution is added, is subsequently added into the cream of amine-modified epoxy resin obtained in Production Example 4 It 7.5 parts of liquid (being scaled resin solid content) and mixes, is further added and (is calcined as 8 parts of Satintone of carbon black of pigment Kaolin) 86.6 parts, pigment dispersion paste material was obtained with 2000rpm stirring 1 hour at 40 DEG C with sand mill.

It is added in 99.5 parts of ion exchange water as ingredient (D)C508 (strong cation polyacrylamide Polyimide resin MTCompany manufactures number-average molecular weight: about 800 ten thousand) 0.5 part, stirring 60 minutes, is contained at normal temperature There is the preparation solution of polyacrylamide resin.

Then, to the above-mentioned preparation of addition in 250 parts of the amine-modified epoxy resin lotion of Production Example 4 (solid component 40%) 4 parts of preparation solution, using obtained substance as F2 lotion.Obtained F2 lotion is used in following estimation of stability, in addition Evaluate stability.

By the pigment thickener of 1539 parts of 1997 parts of ion exchange water above-mentioned F2 lotions and above-mentioned preparation in rustless steel container 464 parts 40 DEG C aging 16 hours, prepare cation electric deposition paint composition.

Cured electrodeposition film is formed similarly to Example 1 using the cation electric deposition paint composition obtained in this way (1)~(3)。

Embodiment 9

It is added 8.3 parts of Dibutyltin oxide and replaces 5.1 parts and 6.5 parts of bismuth oxide of 50% lactic acid aqueous solution, in addition to this, with implementation Example 1 gets similarly the pigment thickener of the 47 mass % of solid component concentration containing Dibutyltin oxide.

Use is used using the pigment thickener obtained in this way, and as ingredient (D)C508 (strong cation Property polyacrylamide resin MTCompany manufactures number-average molecular weight: about 800 ten thousand) preparation contain ingredient (D) 4 parts of preparation solution, obtain cation electric deposition paint composition similarly to Example 1 in addition to this.

Embodiment 10

As chemical conversion treating agent, used as trbasic zinc phosphate chemical conversion treatment solutionSD-5000 (JapanCompany manufactures trbasic zinc phosphate chemical conversion treatment solution) it replacesEC3200 (JapanIt is public Department's manufacture zirconium chemical conversion treating agent), form cured electrodeposition film (1) ~ (3) similarly to Example 3 in addition to this.

Embodiment 11

To pigment dispersing resin (50 mass % of solid component) 60.0 obtained in addition Production Example 1 in 116.6 parts of ion exchange water Mass parts and 100 parts of neodymia, are stirred, and obtain neodymia paste at 40 DEG C using sand mill with 2000rpm stirring 1 hour Material.The solid component concentration of obtained neodymia thickener is 47 mass %.

In other containers, is stirred in 110.1 parts of ion exchange water, mixes 5.1 parts of 50% lactic acid aqueous solution and bismuth oxide 6.5 part.56.7 mass parts of pigment dispersing resin obtained in Production Example 1 are added thereto, at room temperature with 1000rpm stirring 1 Hour.Here, adding 7.1 part 10% of amine-modified epoxy resin lotion, 1.4 parts of aqueous tartaric acid solution obtained in Production Example 4 and stirring It mixes, then, 8 parts of 86.6 parts of Satintone (calcined kaolin) of carbon black as pigment is added, are subsequently added into obtained above 15.3 parts of neodymia thickener, obtain 47 mass %'s of solid component concentration at 40 DEG C using sand mill with 2000rpm stirring 1 hour Pigment thickener.

In addition to using the pigment thickener obtained in this way and using use as ingredient (D)C508(MTCompany manufactures number-average molecular weight: other than about 800 4 parts of preparation solution containing ingredient (D) ten thousand) prepared, with embodiment 1 gets similarly cation electric deposition paint composition.

Comparative example 1

The preparation of cation electric deposition paint composition

In a reservoir, it stirred in 110.1 parts of ion exchange water, mix 5.1 parts of 50% lactic acid aqueous solution and 6.5 parts of bismuth oxide.To It wherein adds 7.1 part 10% of amine-modified epoxy resin lotion, 1.4 parts of aqueous tartaric acid solution obtained in Production Example 4 and stirs, so 8 parts of 86.6 parts of Satintone (calcined kaolin) of carbon black as pigment are added afterwards, using sand mill at 40 DEG C with 2000rpm Stirring 1 hour, obtains the pigment thickener of the 47 mass % of solid component concentration containing bismuth oxide.

2082 parts of ion exchange water, 1454 parts of amine-modified epoxy resin lotion is added into rustless steel container (as F2 cream Liquid) and 464 parts of pigment dispersion paste material obtained above, then, 40 DEG C aging 16 hours, form cation electrodeposition coating group Close object.

Comparative example 2

The preparation of cation electric deposition paint composition

It is prepared in the above-mentioned Production Example 5 of addition into 225 parts of amine-modified epoxy resin lotion (solid component 40%) of Production Example 4 High molecular weight amine-modified epoxy resin (molecular weight: 20,000) 50 parts of preparation solution, as F2 lotion.

In rustless steel container, by what is prepared in 1598 parts of 1938 parts of ion exchange water above-mentioned F2 lotions and comparative example 1 464 parts of pigment thickener 40 DEG C aging 16 hours, prepare cation electric deposition paint composition.

Comparative example 3

Instead of high molecular weight amine-modified epoxy resin, microgel (about 1,000,000 or more PZW-1010 of molecular weight Japan is usedManufacture solid component 30%) 33 parts and 17 parts of preparation F2 lotions of ionized water, it in addition to this must in the same manner as comparative example 2 To cation electric deposition paint composition.

Comparative example 4

Zinc acetate (reagent) is added in the pigment thickener prepared into comparative example 1, makes zinc concentration 0.075%, prepares pigment paste Material.

Other than using pigment thickener obtained above, cation electrodeposition coating group is identically formed with comparative example 2 Close object.

Comparative example 5

Pigment thickener addition hydrofluoric acid titanium (reagent) prepared into comparative example 1 prepares pigment paste so that titanium concentration is 0.05% Material.

Comparative example 6

Hydrofluoric acid zirconium (reagent) is added in the pigment thickener prepared into comparative example 1, makes zirconium concentration 0.05%, prepares pigment paste Material.

Reference example 1

Other than without using ingredient (D), cation electric deposition paint composition is prepared similarly to Example 1.

Reference example 2

Ingredient (D) is replaced using the amine-modified epoxy resin (molecular weight 6000) prepared in comparison manufacturing example 1, in addition to this, with Embodiment 5 gets similarly cation electric deposition paint composition.

The cation electric deposition paint composition and cured electrodeposition film obtained using above-described embodiment and comparative example, into The following evaluations of row.As a result as shown in the table.

Measurement of the electrodeposition coating composition in 23 DEG C of viscosity of the coating

Cation is measured with 60rpm according to JIS K5601 and JIS K7117-1 using Brookfield viscometer (manufacture of TOKIMEC company) Viscosity of the coating of the electrodeposition coating composition at 23 DEG C.

Electrodeposition coating is precipitated in the measurement of 105 DEG C of painting film viscosity

Coated article (cold-rolled steel sheet) is impregnated in cation electric deposition paint composition, 180 seconds electrodeposition coatings is carried out, makes film Thickness is about 15 μm, forms uncured electrodeposition coating.It is washed, removes the electrodeposition coating composition redundantly adhered to. Then, it removes after being attached to the extra moisture on electrodeposition coating surface, it is not dry to take out film immediately, prepare measurement sample Product.For the obtained sample, using measurement of dynamic viscoelasticity device (trade name Rheosol-G3000Company Manufacture) with basic frequency 1Hz shape control 0.5deg measurement viscosity, thus measure the painting film viscosity at 105 DEG C.

Electrodeposition coating is precipitated in the measurement of 105 DEG C of standing viscosity

Coated article (galvanized iron sheet) is impregnated in cation electric deposition paint composition, 180 seconds electrodeposition coatings is carried out, makes film thickness It is about 15 μm, forms uncured electrodeposition coating.It is washed, removes the electrodeposition coating composition redundantly adhered to.It connects , it is not dry to take out film immediately after removing is attached to the extra moisture on electrodeposition coating surface, prepare test sample. The sample that will be obtained uses measurement of dynamic viscoelasticity device (trade name MCR302Company's manufacture), it will shear Speed is set as d (gamma)/dt=0.011/ second, thus the shear viscosity at 105 DEG C of measurement after 300 seconds is measured at 105 DEG C Stand viscosity.

Electrolytic corrosion test at edge (20 μm 40 μm of film thickness)

It replaces the L-type for forming the cured electrodeposition film with 20 μm or 40 μm of film thickness in above-described embodiment and comparative example is dedicated Allowing blade replacement is as test film.

Salt spraytest (35 DEG C × 168 hours) according to JIS Z 2371 (2000) is carried out to the test film, investigates L The number got rusty that the dedicated replacing blade front end of type generates.

It is noted that in this experiment, " the dedicated replacing blade front end of L-type " refers to from the vertex of blade to replacement knife The width of piece ontology direction 5mm.Above-mentioned width includes two sides of surface side and back side, and surface back side adds up to 10mm width. It should " edge part " of " the dedicated replacing blade front end of L-type " quite in this manual.

For example, when the number got rusty generated in the dedicated replacing blade front end of L-type in following evaluations is 30, L-type The length of dedicated replacing blade is that the surface back side of the dedicated replacing blade front end width of 100mm (10cm) L-type adds up to 10mm (width 1cm), therefore the dedicated every 1cm in replacing blade front end of L-type²The number got rusty be

30/10cm²=3/cm²。

Evaluation criteria

◎: it does not get rusty

Zero: less than 10

(the dedicated every 1cm in replacing blade front end of L-type²The number got rusty less than 1/cm²)

Zero △: 10 more than and less than 30

(the dedicated every 1cm in replacing blade front end of L-type²The number got rusty be 1/cm²More than and less than 3/cm²)

△: 30 or more ~ less than 50

(the dedicated every 1cm in replacing blade front end of L-type²The number got rusty be 3/cm²More than and less than 5/cm²)

△ ×: 50 or more ~ less than 100

(the dedicated every 1cm in replacing blade front end of L-type²The number got rusty be 5/cm²More than and less than 10/cm²)

×: 100 or more

(the dedicated every 1cm in replacing blade front end of L-type²The number got rusty be 10/cm²More than).

The ocular estimate (Ra flatness) of cured electrodeposition film

For the surface roughness of cured electrodeposition film obtained above, according to JIS-B0601 in-service evaluation type rough surface Spend the arithmetic mean roughness of measuring machine (Mitsutoyo company manufactures SURFTEST SJ-201P) measurement roughness curve (Ra).It is measured 7 times using the sample for the boundary (zoning number 5) for introducing 2.5mm width, by removing the flat of maximum value and minimum value Obtain Ra value.It may be said that the Ra value is smaller, concave-convex fewer, appearance of film is better.It is noted that JIS-B0601 is opposite In the Japanese Industrial Specifications of ISO 4287.

Ocular estimate (irregular colour)

Cation electric deposition paint composition obtained in embodiment and comparative example is stirred with 1000rpm, then stops stirring, After steel plate is horizontally all buried, keep 3 minutes, start apply voltage, with boosting 30 seconds, reach 180V after kept for 150 seconds Condition apply voltage, uncured electro-deposition epithelium is precipitated on coated article (cold-rolled steel sheet).The uncured electricity that will be obtained Deposition epithelium is heating and curing 15 minutes at 160 DEG C, obtains the electrodeposition coating plate with electrodeposition coating.About electrodeposition coating Plate, the appearance of film for visually observing top and bottom have without exception evaluated.Evaluation criteria is as follows.

Evaluation criteria

Zero: top and bottom all have uniform appearance of film, without unevenness.

Zero △: although top and bottom epithelium has the part that can slightly see unevenness, but has outside almost uniform film on the whole See (practical above there is no problem)

△: top and bottom epithelium has the part that can see unevenness, has non-uniform appearance of film (practical problematic) on the whole

×: uneven (practical problematic) is clearly visible on horizontal following side envelope.

The storage stability of coating

Use F2 lotion and pigment used in the preparation in each embodiment and the cation electric deposition paint composition of comparative example Thickener carries out storage stability evaluation.

F2 lotion: after solid component is adjusted to 35 mass %, 40 DEG C keeping 4 weeks.It is commented after keeping with following benchmark Valence.

Pigment thickener: by pigment thickener used in coating preparation 40 DEG C keeping 4 weeks.After keeping, with the progress of following benchmark Evaluation.

Evaluation criteria

Both zero: F2 lotion and pigment thickener have almost no change, and can be evaluated to stablize.

At least one party in △: F2 lotion and pigment thickener observes that viscosity slightly increases, but by being again stirring for and extensive Multiple, practical above there is no problem.

×: at least one party's viscosity increases big in F2 lotion and pigment thickener, is determined as that paint stability is poor.

In the case where cation electric deposition paint composition using embodiment, obtain outside good rust-preventing characteristic and film It sees.In addition, paint stability is also excellent.Moreover, the cation electric deposition paint composition of embodiment is in setting cured electrodeposition Under the either case that 20 μm and 40 μm of film thickness of the film thickness of film, good edge part rust-preventing characteristic is obtained.

Comparative example 1 is free from the 3rd group element compound (C) and cation or non-ionic resin (D) any one example Son.In the example, edge part rust-preventing characteristic is substantially deteriorated.

Comparative example 2 is free from the example of the 3rd group element compound (C).The edge part rust-preventing characteristic of the example is also poor.

Comparative example 3 is free from the 3rd group element compound (C) and using acrylic acid series microgel instead of ingredient (D) Example.The edge part rust-preventing characteristic of the example is poor.

Comparative example 4 ~ 6 is the example that the 3rd group element compound (C) is replaced using other metallic compounds.In these examples, Although how much edge part rust-preventing characteristic improves, the appearance of film of cured electrodeposition film is deteriorated.

It is noted that when preparation of cation electric deposition paint composition, confirms apparent viscosity in comparative example 4 ~ 6 Rise, therefore coating storage stability test same as other embodiments comparative example could not be carried out.

Reference example 1 is the example containing the 3rd group element compound (C) but without containing cation or non-ionic resin (D). In the example, although obtaining rust-preventing characteristic to a certain degree, the film thickness of cured electrodeposition film thickens, edge part rust-preventing characteristic Difference.

Reference example 2 is containing the 3rd group element compound (C) but the molecular weight of cation or non-ionic resin is less than 10, 000 example.Although the example has obtained rust-preventing characteristic to a certain degree, but the film thickness of cured electrodeposition film thickens, edge Portion's rust-preventing characteristic is poor.

Industrial applicability

Electrodeposition coating is carried out by using cation electric deposition paint composition of the invention, it is special rust-preventing characteristic can be formed Be edge part rust-preventing characteristic it is excellent and with excellent appearance of film cured electrodeposition film.Cationic electrodeposition of the invention Coating composition can suitably use in the formation of for example thick cured electrodeposition film.Through the invention to electrodeposition coating The cured electrodeposition film of middle formation provides diversity.

Claims

1. cation electric deposition paint composition is containing amine-modified epoxy resin (A) curing agent (B) the 3rd race's element The cation electric deposition paint composition of object (C) and cation or non-ionic resin (D) are closed,

2. cation electric deposition paint composition according to claim 1, wherein above-mentioned cation or non-ionic resin It (D) is a kind or a kind or more in polyacrylamide resin chitosan resin and amine-modified epoxy resin.

3. cation electric deposition paint composition according to claim 2, wherein above-mentioned polyacrylamide resin be sun from Sub- property polyacrylamide resin.

4. cation electric deposition paint composition described according to claim 1 ~ any one of 3, wherein above-mentioned 3rd race's element Compound (C) is the mixture hydroxide selected from lanthana lanthanum hydroxide neodymia neodymium hydroxide lanthana and organic acid 1 kind or 1 in the mixture neodymium hydroxide of the mixture neodymia and organic acid of lanthanum and organic acid and the mixture of organic acid Kind or more.

5. cation electric deposition paint composition described according to claim 1 ~ any one of 4, wherein above-mentioned cation electrodeposition is heavy Product coating composition be precipitated electrodeposition coating 105 DEG C painting film viscosity be 10Pa s hereinafter, and

6. cation electric deposition paint composition described according to claim 1 ~ any one of 5, wherein above-mentioned cation electrodeposition is heavy Product coating composition is 10mPa s or less in 23 DEG C of viscosity of the coating.

7. cation electric deposition paint composition described according to claim 1 ~ any one of 6, wherein above-mentioned cation electrodeposition is heavy Product coating composition also contains bismuth compound, and the average grain diameter of above-mentioned bismuth compound is 1 ~ 500nm.

8. cured electrodeposition coating film-forming methods comprising the cationic electrodeposition described in any one of claim 1 ~ 7 applies Coated article is impregnated in feed composition and carries out electrodeposition coating, is then heating and curing, is thus formed 25 ~ 50 μm of film thickness on coated article Cured electrodeposition film process.

9. coating film-forming methods according to claim 8, wherein above-mentioned coated article has edge part, and to shape At cured electrodeposition film coated article carry out salt spraytest when, edge painting portion 1cm²Get rusty and number occurs be less than 5/cm²。